Fe3 O4 - DergiPark

Turkish Journal of Chemistry
http://journals.tubitak.gov.tr/chem/
Research Article
Turk J Chem
(2014) 38: 488 – 503
¨ ITAK
˙
c TUB
⃝
doi:10.3906/kim-1307-50
Selective oxidation of sulfides and hydrocarbons with H 2 O 2 over manganese
catalyst supported on nanoparticles
Massomeh GHORBANLOO1,∗, Roghayeh TARASI1 ,
Jun TAO2 , Hidenori YAHIRO3
1
Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan, Iran
2
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry
and Chemical Engineering, Xiamen University, Xiamen, Fujian Province, P. R. China
3
Department of Applied Chemistry, Faculty of Engineering, Ehime University, Matsuyama, Japan
Received: 19.07.2013
•
Accepted: 30.11.2013
•
Published Online: 14.04.2014
•
Printed: 12.05.2014
Abstract: A new magnetically separable catalyst consisting of binuclear Mn(II) complex [Mn 2 (HL) 2 (H 2 O) 4 ], HL =
2-[(2-hydroxy-benzylidene)-amino]-3-(4-hydroxyphenyl)-propionic acid, supported on (3-chloropropyl)-trimethoxysilane
(CPTMS) functionalized silica-coated magnetic nanoparticles (MNPs) was prepared. The synthesized catalyst was
characterized by several physico-chemical and spectroscopic methods. This immobilized complex was found to be an
efficient heterogeneous catalyst for the oxidation of different sulfides and hydrocarbons using hydrogen peroxide (H 2 O 2 )
as an oxidant. The catalyst is readily recovered by simple magnetic decantation and can be recycled several times with
no considerable loss of catalytic activity.
Key words: Magnetic, heterogeneous catalyst, binuclear, nanoparticles, oxidation, H 2 O 2
1. Introduction
Nanomagnetic systems have been extensively used in biomedical and pharmaceutical applications. 1 Magnetic
nanoparticles (MNPs) of iron oxides have attracted much attention because of their unique properties and
potential applications in different fields, such as magnetically assisted drug delivery and magnetic resonance
imaging (MRI) contrast agents. 2 Moreover, MNPs are good supports for immobilization of homogeneous
catalysts. 3 Therefore, catalytic systems with MNP supports have been successfully utilized in catalyzing a
broad series of chemical reactions such as oxidation 4 and polymerization. 5
The oxidation of organic sulfides to the corresponding sulfoxides is one of the essential functional group
transformations in organic synthesis. 6 Organic sulfoxides are important synthetic intermediates for the production of chemically and biologically active molecules and also show promise as remedial agents. 7
Catalytic oxidation of hydrocarbons is also of great importance in the chemical industry for the exchange from petroleum-based feed stocks to valuable chemicals such as diols, epoxides, alcohols, and carbonyl
compounds. 8 For example, benzaldehyde, a characteristic product of toluene oxidation, and aromatic ketones
are very important starting materials for the preparation of intermediates in perfumery and pharmaceuticals. 9
Production of aromatic ketones by Friedel–Crafts acylation of aromatics leads to the production of toxic and
corrosive wastes. Lately, there has been increased attention on finding clean, economical catalytic processes for
synthesizing ketones via benzylic oxidation of alkyl aromatics. 10
∗ Correspondence:
488
m ghorbanloo@yahoo.com
GHORBANLOO et al./Turk J Chem
There are several oxidants such as hydrogen peroxide (H 2 O 2 ), tert-butylhydroperoxide (TBHP), and
iodosylbenzene (PhIO) for oxidation. However, H 2 O 2 is regarded as a perfect ‘green’ oxidant, because of
its absence of toxic by-products. Hence, robust, efficient, and recyclable heterogeneous catalysts have been
developed for activation of H 2 O 2 for oxidation of substrates Heterogeneous oxidation catalysts are notable, due
to their easy handling, product separation, catalyst recovery, and reduced waste. Fixation of such complexes
by covalent attachment to a functionalized support provides stable heterogeneous catalysts. 11 For this purpose,
MNPs are potential candidates, and catalytic systems based on super-paramagnetic nanoparticles as a support
have been discussed. 12,13 One of the major advantages of a catalytic system anchored in MNPs is that they can
be well isolated by a simple magnetic separation procedure. However, MNPs have a tendency to aggregate in
liquid media owing to their magnetic dipole–dipole interaction, 3 and so their surface area and magnetism may
be decreased. Therefore, coating with a thin layer of silica has been used to stabilize bare MNPs to avoid their
agglomeration in solutions. 3 Silica is one of the best materials for coating of MNPs because of its high chemical
stability and easy functionalization. 14−16 There are numerous reports on the preparation and applications of
silica-coated MNPs. 17−19
In this work, the catalytic performance of Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] was checked by sulfide and
hydrocarbon oxidation with 30% aqueous H 2 O 2 . We also compared the catalytic activity of our earlier reported
catalysts 20 and Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]) catalyst in the oxidation of methyl phenyl sulfide.
2. Results and discussion
2.1. Synthesis and immobilization
The Schiff base ligand H 3 L was synthesized by the condensation of salicylaldehyde with L-tyrosine in 1:1 molar
ratio in methanol. 21 Its manganese complex was synthesized and characterized according to our previously
reported method 20 (Scheme 1).
The complex was immobilized on SiO 2 -coated magnetite nanoparticles using (3-chloropropyl)-trimethoxysilane as a linker. Immobilization of the complex involves reaction of their phenolic groups with (3-chloropropyl)trimethoxysilane (CPTMS) (Scheme 1). The CPTMS moiety is bonded strongly to Fe 3 O 4 @SiO 2 by means of
a covalent bond that prevents/reduces leaching of the catalyst in polar solvents. We washed these compounds
to ensure that only the covalently attached molecules remained on the support.
2.2. Characterization
The FTIR spectrum of H 3 L ligand is shown in Figure 1. There are no bands at 3245 and 1745 cm −1 due to
the υ (NH 2 ) group of amino acids and υ (C=O) of salicylaldehyde, respectively. In its place, a new important
band at 1613 cm −1 owing to azomethine υ (C=N) linkage appeared in this ligand. 21
Figure 2 shows the FTIR spectra of the heterogeneous compounds: Fe 3 O 4 , Fe 3 O 4 @SiO 2 , and Fe 3 O 4 @
SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ]. The FTIR spectrum of Fe 3 O 4 (Figure 2a) exhibited the expected Fe–O stretching
absorption at 580 cm −1 . This peak appears in all the IR spectra of heterogeneous compounds, which are
assigned to the Fe–O group. In IR spectra of the Fe 3 O 4 /SiO 2 and Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ], the
absorption intensity of the Fe–O group decreases with the addition of the silica portion 22 and a strong absorption
intensity of the Si–O–Si group appears owing to the silica coat. In Figure 2b, the bands at 477, 950, and 1098
cm −1 are assigned to δ (Si–O–Si), ν (Si–OH), and νas (Si–O–Si), respectively. 23
The FTIR spectrum of the supported catalyst, Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ] (Figure 2c), exhibits
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GHORBANLOO et al./Turk J Chem
OH
OH2
O
O HO
OH
NH2
+ O
OH
HO
O OH2
Mn(OAC)2.4H2 O
HO
Mn
N
5 h reflux
N
O
N
O
O
Mn
OH
H2O O
O
H2O
OH
SiO2
O
Fe3O4
TEOS
CPTMS
Fe3 O4
Fe3O4
O
Si
Cl
O
OH
O OH 2
O
Fe3O4
O
N
Si
Cl
Mn2(HL) 2(H2O)4
CH2Cl 2, ref 24 h
O
O
OH2
Mn
O
O
H2O
Mn
O
N
H2O O
O
Fe3O 4
O
Si
O
O
Scheme 1. Schematic representation of the formation of e 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ].
the new characteristic bands of the complex units at 1647 (C=N), 1596 (νas (COO)), 1388 ( νs (COO)), ∼ 400,
and ∼ 530 cm −1 υ (M–N) and υ (M–O) associated with silica matrix bands at 1097, 809, and 477 cm −1 and
magnetite matrix band at ∼580 cm −1 . Typically, a broad band with high intensity in the range of 3500–3400
cm −1 corresponded to the O–H vibration of SiO–H groups and HO–H of adsorbed water. 24 Hence, the FTIR
characterization confirmed the successful immobilization of the Mn(II) complex to the modified Fe 3 O 4 @SiO 2
nanoparticles.
The morphologies of Fe 3 O 4 , Fe 3 O 4 @SiO 2 , and Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ] were characterized
with scanning electron microscopy. As shown in Figure 3, the nanoparticles sizes of Fe 3 O 4 , Fe 3 O 4 @SiO 2 , and
Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ] were about 18, 39, and 63 nm, respectively. Moreover, as it is shown, these
nanoparticles had spherical shapes.
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GHORBANLOO et al./Turk J Chem
c
b
%T
%T
a
4000
3500
3000
2500
2000
1500
1000
Wavenumber/cm-1
Figure 1. FTIR spectrum of H 3 L.
500
3500
3000
2500
2000
1500
1000
500
Wavenumber/cm-1
Figure 2. FTIR spectra of a) Fe 3 O 4 ,
b) Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ], c) Fe 3 O 4 @SiO 2 .
Figure 3. SEM image of a) Fe 3 O 4 @ SiO 2 /[Mn 2 L(HL) (H 2 O) 4 ], b) Fe 3 O 4 @SiO 2 , c) Fe 3 O 4 .
Magnetization data for Fe 3 O 4 , Fe 3 O 4 @SiO 2 , and Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ] were collected
between –5 and +5 T at room temperature and the M versus H curves are shown in Figure 4. All samples show
super-paramagnetic properties, indicating the retaining of the nanostructural nature of Fe 3 O 4 . It can be seen
from the loops in Figures 4a–c that the saturation magnetization (MS) of Fe 3 O 4 , Fe 3 O 4 @SiO 2 , and Fe 3 O 4 @
SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ] was 66.35, 53.51, and 47.67 emu/g, respectively. Although the mass saturation
magnetization in the last 2 composites decreased due to the contribution of the nonmagnetic silica shell and
functionalized groups, 25 they still could be efficiently separated from solution media with a permanent magnet.
The decrease in size of MNPs and/or the increase in mass of the monolayer that was nonmagnetic on
them may have reduced saturation magnetization. 25 This can be interpreted either by the occurrence of a dead
magnetic layer originated by the demagnetization of the surface spins 26 or disordered a spin structure at the
surface. 27,28
When particle size decreases, the ratio of surface to total number of spins increases, which makes the
contribution of surface spins to overall magnetization considerable. The super-exchange interaction between
Fe–O–Fe ions weakens and the total magnetization of the particle decreases if the surface spins are disordered
or misaligned. Additionally, it was established that the saturation magnetization became lower owing to the
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GHORBANLOO et al./Turk J Chem
high molecular weight of complex. This may be explained by the high molecular weight of complex thickening
the coating layer, which lowers the content of Fe 3 O 4 . 29
80
60
M(emu/g)
40
20
0
-20
-40
a
b
c
-60
-80
-6
-4
-2
0
2
4
6
H(T)
Figure 4. Hysteresis loops of a) Fe 3 O 4 @ SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ], b) Fe 3 O 4 @SiO 2 , c) Fe 3 O 4 .
2.3. Catalytic activity studies
The catalytic activity of the catalyst was checked for oxidation of sulfides and hydrocarbons with 30% aqueous
H2 O2 .
In these reactions, H 2 O 2 should be used carefully, due to the possibility of overoxidation. 30 The effect
of different amounts of H 2 O 2 was investigated with a fixed amount of substrate (1.0 mmol) and catalyst
Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] (6.4 mg, 0.0016 mmol) in 3 mL of CH 3 CN at 60 ± 1 ◦ C.
For sulfoxidation, as shown in Table 1 (entries 1–3), the conversion and selectivity drastically increased
with the molecular ratio of H 2 O 2 to methyl phenyl sulfide, until the ratio was equal to 3. The catalytic
oxidation gave 75% sulfoxide with 3 mmol of H 2 O 2 in 60 min (Table 1, entry 3). The excess H 2 O 2 required
in this catalytic system can be attributed to its decomposition in the presence of the catalyst. 20
In control experiments without the catalyst, the yield of sulfoxide was low (Table 1, entry 4). Furthermore,
when the catalyst was replaced by Fe 3 O 4 @SiO 2 , extensive peroxide decomposition was observed and no
sulfoxide was obtained (Table 1, entry 5).
Next, the catalytic oxidation was studied in various solvents (Table 2). The catalytic activity decreases in the
order acetonitrile (dielectric constant ε/ ε0 = 37.5) > methanol (32.7) > chloroform (5.5) at 60 ◦ C. Chloroform
is not miscible with aqueous H 2 O 2 , which could also be the reason for low catalytic efficiency. However, the
best performance of the catalyst was observed in acetonitrile, which is therefore the solvent of choice. The
oxidation was significantly influenced by the reaction temperature (Table 3, entries 1–3). The optimum results
were obtained at 60
◦
C; higher temperatures gave lower yields (Table 3, entry 3). It seems likely that higher
temperatures facilitate the decomposition of H 2 O 2 . 31
A variety of salen complexes 32 are able to catalyze the oxidation of sulfides to sulfoxides with H 2 O 2 ,
but a drawback of these systems is often the use of chlorinated solvents or anhydrous H 2 O 2 in ethanol as well
as overoxidation to sulfones.
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GHORBANLOO et al./Turk J Chem
Table 1. Oxidation of methyl phenyl sulfides by the Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]/H 2 O 2 .
No.
Substrate
Sulfoxide/Sulfone
yield (%)
H2 O2 :Substrate
molar ratio
Sulfoxide
selectivity (%)c
23:4
1:1a
91
52:0
2:1a
100
75:0
3:1a
100
11:25
3:1d
30
0
3:1e
—
S
1
S
2
S
3
S
4
S
5
a
Reaction conditions: catalyst 6.4 mg (0.0016 mmol), MeSPh 1 mmol, CH 3 CN 3 mL, temperature 60 ± 1
60 min,
b
Conversions are based on the starting substrate;
◦
c
◦
C, time
sulfoxide selectivity: %sulfoxide/(sulfoxide + sulfone);
d
Without catalyst; reaction temperature 60
e
Fe 3 O 4 @SiO 2 (0.0016 mmol), MeSPh 1.0 mmol, CH 3 CN 3 mL, time 2 h, temperature 60 ± 1
C, MeSPh 1.0 mmol, CH 3 CN 3 mL, reaction time 2 h, H 2 O 2 3 mmol;
◦
C.
Table 2. Solvent effect on the oxidation of methyl phenyl sulfide with Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]/H 2 O 2 .a
Entry
1
2
3
a
Solvent
CHCl3
CH3 OH
CH3 CN
Conv. (%)b
13
63
75
Sulfoxide selectivity (%)c
100
100
100
Reaction conditions: catalyst 6.4 mg (0.0016 mmol), MeSPh 1.0 mmol, solvent 3 mL, H 2 O 2 3 mmol, time 60 min,
temperature 60 ± 1
◦
C; b Conversions are based on the starting substrate; c sulfoxide selectivity: %sulfoxide/(sulfoxide
+ sulfone).
Table 3. Temperature effect on the oxidation of methyl phenyl sulfide with Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]/H 2 O 2 .a
Entry
1
2
3
a
b
Temp (◦ C)
25
60
80
Conv. (%)b
11
75
66
Sulfoxide selectivity (%)c
100
100
92
Reaction conditions: catalyst 6.4 mg (0.0016 mmol), MeSPh 1.0 mmol, CH 3 CN 3 mL, H 2 O 2 3 mmol, time 60 min;
Conversions are based on the starting substrate; c sulfoxide selectivity: %sulfoxide/(sulfoxide + sulfone).
Comparison of the homogeneous and heterogeneous (nanomagnetic and bulk silica gel particles) systems
reveals that the heterogeneous catalysts exhibit lower activity than the homogeneous catalyst (Table 4, entries
1, 2). It seems likely that the use of a supported manganese catalyst in the present case gives rise to additional
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GHORBANLOO et al./Turk J Chem
problems related to the probable dismutation of H 2 O 2 by the inorganic support. This would explain why
only a few systems based on supported manganese catalysts and H 2 O 2 have been reported for oxidation
reactions. 33 Related difficulties were earlier encountered for Mn(III)– and Mo(IV)–salen complexes immobilized
on mesoporous silica gel. 34
Table 4. Oxidation of alkyl phenyl sulfides by the Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]/H 2 O 2 and comparing catalytic
activity of Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] and [Mn 2 L(HL)(H 2 O) 4 ] in MeSPh oxidation.
No.
Substrate
Sulfoxide/Sulfone
yield (%)b
H2 O2 :Substrate
molar ratio
Sulfoxide
selectivity (%)c
75:0
3:1a
100
95:0
3:1d
100
23:0
3:1a
100
34:0
3:1a
100
S
1
S
2
S
3
S
4
a
Reaction conditions: catalyst 6.4 mg (0.0016 mmol), RSPh 1 mmol, CH 3 CN 3 mL, temperature 60 ± 1
60 min;
b
Conversions are based on the starting substrate.;
c
◦
C, time
sulfoxide selectivity: %sulfoxide/(sulfoxide + sulfone);
Reaction conditions: Homogeneous catalyst 1 mg, MeSPh 1 mmol, CH 3 CN 3 mL, temperature 60 ± 1
min.
d
◦
C, time 120
Table 4 shows that the homogeneous complex in solution was more active for sulfide oxidation than
the immobilized counterparts with an equivalent quantity. The lower activity of the anchored complexes
may be due to diffusion problems associated with the supports. However, activity and chemoselectivity of
Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] were higher than those of SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]. This may be related to the nanoparticle nature of the Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] with high specific surface area,
which in turns increases the catalytic activity and selectivity. 35 Similar results have been reported by Tangestaninejad et al.; the catalytic activity of [Mn(salophen)Cl] supported on the polystyrene was lower than that on
MWCNT nanoparticles 35 and Mn(TPyP)/SiO2–Fe 3 O 4 was a much more efficient catalyst than polystyrenebound Mn(TPyP)OAc. 36
In this catalytic system, the activity of the heterogeneous Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] catalyst
is lower than that of the homogeneous [Mn 2 L(HL)(H 2 O) 4 ] one, which can be attributed to diffusion problems
associated with the supports. Anyway, the activity of heterogeneous Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]
catalyst is higher than those of similar homogeneous manganese complexes such as biotinylated manganese–salen
complexes for aqueous sulfoxidation by using H 2 O 2 as an oxidant. 37
The oxidation of further sulfides was carried out under optimized conditions (Table 4, entries 3, 4). Ethyl
phenyl sulfide and n-butyl phenyl sulfide were oxidized by catalyst/H 2 O 2 to the corresponding sulfoxides; for
these 2 substrates the oxidation yields (23% and 34%, respectively) were lower than the methyl phenyl sulfide
oxidation (75%). This can be related to their high steric hindrance.
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GHORBANLOO et al./Turk J Chem
Finally, it is notable that our catalytic system (catalyst/H 2 O 2 ) is simple and efficient for oxidation
of sulfides in comparison with other Mn catalysts, 35,38,39 because our catalytic system shows high conversion
without using other additive materials like co-catalysts.
The activities of the catalyst were also tested for the oxidation of toluene, cyclohexane, and ethyl benzene,
because oxidations of alkylbenzenes are important transformations in chemical synthesis. 40 In many cases of
alkylbenzene oxidation, selectivity is low because of the formation of various by-products. For example, it has
been reported that the oxidation of toluene leads to the formation of benzaldehyde, benzyl alcohol, cresols, and
benzoic acid because of oxidations of the methyl group and/or of the aromatic ring. 41 Thus, the design of an
efficient process for the selective oxidation of alkylbenzenes appears to be an important task.
In order to achieve suitable reaction conditions for maximum transformation of toluene as well as better
selectivity for the formation of benzaldehyde, the effects of H 2 O 2 concentration (mole of H 2 O 2 per mole of
toluene), catalyst amount, and temperature were studied.
The effect of H 2 O 2 concentration on the toluene oxidation reaction is shown in Table 5. Benzaldehyde
was formed as the major product, while benzyl alcohol and benzoic acid were generated as minor ones. No
oxidation of the aromatic ring was observed. Four different molar ratios of H 2 O 2 to toluene were used (1:1, 2:1,
3:1, and 4:1 mol) in which the amount of toluene was kept fixed at 1 mmol in 3 mL of MeCN (Table 5, entries
1–4). The percentage toluene conversion increased with the increment in H 2 O 2 to toluene ratio, until the ratio
was equal to 3. The catalytic oxidation gave 21% conversion with good selectivity to benzaldehyde (80%), with
3 mmol of H 2 O 2 in 2 h (Table 5, entry 3). However, with ratios higher than 3:1, the excess amount of H 2 O 2
caused low selectivity to benzaldehyde, 72.4%, and caused 20.7% and 6.9% selectivity to benzyl alcohol and
benzoic acid (Table 5, entry 4), respectively.
Table 5. Effect of oxidant/substrate molar ratio on toluene oxidation. a
H2 O2 : Substrate
molar ratio
1:1
2:1
3:1
4:1
3:1
3:1
Entry
1
2
3
4
5d
6e
a
7
15
21
29
3
0
Selectivity(%)
Benzaldehyde
57
76.5
80
72.4
54
—
Benzyl alcohol
43
23.5
20
20.7c
46
—
Reaction conditions: Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] (0.0016 mmol), toluene 1.0 mmol, CH 3 CN 3 mL, time 2
h, temperature 60 ± 1
d
Conversion.b (%)
◦
C,
b
Conversions are based on the starting substrate,
Without catalyst; reaction temperature 60
◦
c
The other product is benzoic acid,
C, toluene 1 mmol, CH 3 CN 2 mL, reaction time 2 h, H 2 O 2 3 mmol;
Fe 3 O 4 @SiO 2 (0.0016 mmol), toluene 1.0 mmol, CH 3 CN 3 mL, time 2 h, temperature 60 ± 1
◦
e
C.
A previous study on the catalytic transformation of toluene by t-BuOOH in the presence of Mn(salen)
demonstrated that the catalyst immobilized on the polymeric membrane exhibited a slightly lower activity than
the unsupported catalyst. 42 The addition of an acid promoter was reported to lead to much higher activity and
selectivity for both Mn(salen) and Mn(salen)-PM. 42
In control experiments, the same as sulfoxidation, without the catalyst, the yield of oxidation was
low (Table 5, entry 5). Furthermore, when the catalyst was replaced by Fe 3 O 4 @SiO 2 , due to peroxide
decomposition no toluene oxidation was achieved (Table 5, entry 6).
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GHORBANLOO et al./Turk J Chem
The amount of catalyst has a significant effect on the oxidation of toluene. Five different amounts of
catalyst, viz., 12, 14, 16, 18, and 20 ( ×10 −4 mmol), were used, with all other reaction parameters fixed: namely
temperature (60
◦
C), toluene (1 mmol) to H 2 O 2 (3 mmol), and reaction time (2 h). The results are shown
in Table 6, entries 1–5, indicating 5%, 13%, 21%, 30%, and 24% conversion corresponding to 12, 14, 16, 18,
and 20 × 10 −4 mmol catalyst, respectively. The lower conversion of toluene into aldehyde with 12 × 10 −4
and 14 × 10 −4 mmol catalyst may be because of fewer catalytic sites. 9 The maximum percentage conversion
was observed with 18 × 10 −4 mmol catalyst, but a further increase of catalyst to 20 × 10 −4 mmol resulted
in lower conversion, because of adsorption/chemisorption of the 2 reactants on separate catalyst particles, thus
reducing the chance to interact. 36,43,44 There was also a sharp decrease in the selectivity to benzaldehyde as the
catalyst amount increased to 0.0018 mmol. Beyond 0.0018 mmol catalyst, the conversion obviously declined,
which indicated that the excess catalyst can accelerate rapid decomposition of H 2 O 2 , limiting further oxidation
of toluene. 45
Table 6. Effect of catalyst amount on toluene oxidation. a
Entry
Temp (◦ C)
Time (h)
Conversion (%)
1
2
3
4
5
12
14
16
18
20
3
3
2
2
2
5
13
21
20
24
Selectivity
Aldehyde
70
76
80
82
62.5
(%)
Alcohol
30
24
20
18
37.5
Reaction conditions: a) catalyst Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]; reaction temperature 60 ± 1 ◦ C, toluene 1 mmol,
CH 3 CN 3 mL, H 2 O 2 3 mmol.
Temperature also had a remarkable effect on the conversion of toluene in the range from 25 to 60 ◦ C;
also the aldehyde selectivity strongly depended on the temperature. The conversion of toluene increased with
increasing reaction temperature from 25 to 80 ◦ C (Table 7, entries 1–3). Beyond 60 ◦ C, the conversion slightly
decreased (Table 7, entry 3). This was possibly caused by acceleration of H 2 O 2 decomposition at higher
temperature. As a main product of toluene oxidation, the selectivity to benzaldehyde was rapidly declined,
while the selectivity to other products such as benzyl alcohol and benzoic acid was increased with the rising
temperature. As the temperature rose, the consumed rate of benzaldehyde exceeded its generating rate and the
generating rate of benzyl alcohol was faster than that of its conversion into benzaldehyde at higher temperature.
However, the benzaldehyde consumption led to an increase in the amount of benzoic acid. 9
Table 7. Temperature effect on the oxidation of toluene with Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]/H 2 O .a
2
a
Entry
Temp (◦ C)
Conversion (%)b
1
2
3
25
60
80
7
30
19
Selectivity
Aldehyde
42.8
82
52.6
(%)
Alcohol
57.2
18
31.6c
Reaction conditions: catalyst (0.0018 mmol), toluene 1.0 mmol, CH 3 CN 3 mL, H 2 O 2 3 mmol, time 2 h.
c
are based on the starting substrate; The other product is benzoic acid.
496
b
Conversions
GHORBANLOO et al./Turk J Chem
The oxidation of ethyl benzene and cyclohexane was carried out under optimized conditions.
The oxidation takes place on the side chain of ethylbenzene and the results of the % conversion of
ethylbenzene (38%) and % selectivity to acetophenone (92%) and benzaldehyde (8%) are presented in Table 8,
entry 2. According to the results, the selectivity of catalyst to acetophenone is higher than to the other products,
possibly due to the fact that the rate of acetophenone production was greater than that of benzaldehyde
production since dehydration is easier than the elimination of methanol. Therefore, the amount of benzoic acid
production was trace. 45
Table 8. Oxidation of hydrocarbons by the Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]/H 2 O a2 and [Mn 2 (HL) 2 (H 2 O) 4 ]. b
a
Entry
Hydrocarbon
1
2
3
Toluene
Ethylbenzene
Cyclohexane
Conversion (%)b
(heterogeneous/homogeneous)
30/42
38/50
24/35
Selectivity (%)
(heterogeneous/homogeneous)
82/62f
18/31g 0/7h
i
92/76
8/16f 0/8h
d
79.2/57.2
20.8/42.8e
Reaction conditions: Heterogeneous catalyst (0.0018 mmol), alkane 1.0 mmol, CH 3 CN 3 mL, H 2 O 2 3 mmol, tem-
perature 60 ± 1
◦
C, time 2 h; b Reaction conditions: Homogeneous catalyst (0.0018 mmol), alkane 1.0 mmol, CH 3 CN
3 mL, H 2 O 2 3 mmol, temperature 60 ± 1
erogeneous/homogeneous conditions
benzaldehyde
g
d
◦
C, time 3 h;
c
Conversions are based on the starting substrate for het-
The product is cyclohexanone;
The product is benzylalcohol;
h
e
The product is cyclohexanol;
The product is benzoic acid;
i
f
The product is
The product is acetophenone.
In this work, in the oxidation of cyclohexane, an overall conversion of 24% was observed, with 79%
selectivity to cyclohexanol and 21% to cyclohexanone (Table 8, entry 3). In this respect, the activity and/or
selectivity of this catalyst is much better than that of Mn(III)salophen and Mn(III)salophen-PSI. 46
Comparison of the homogeneous and heterogeneous systems reveals that the heterogeneous catalysts
exhibited lower activity than the homogeneous catalyst (Table 8, entries 1–3). It seems likely that the use of
a supported manganese catalyst in the present case gives rise to additional problems related to the probable
dismutation of H 2 O 2 by the inorganic support. However, it is notable that our heterogeneous catalyst showed
higher selectivity than its homogeneous counterpart (Table 8, entries 1–3).
Various homogeneous and heterogeneous Mn catalysts have been used for the oxidation of cycloalkanes
with H 2 O 2 and t-BuOOH. 47,48 However, none of the reported catalysts showed such high activity and/or
selectivity as [Mn 2 (HL) 2 (H 2 O) 4 ] or Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ].
2.4. Proposed mechanism for the oxidation of ethylbenzene with H 2 O 2 over the Fe 3 O 4 @SiO 2 /
[Mn 2 L(HL)(H 2 O) 4 ]
The mechanism for the oxidation of ethylbenzene with H 2 O 2 over the Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ]
catalyst proceeded in several steps as shown in Scheme 2. H 2 O 2 was activated by coordinating with the
immobilized Mn(II)–Schiff base complexes, that is, the activated distant oxygen of co-coordinated H 2 O 2 reacted
with ethylbenzene to yield the products. This type of intramolecular hydrogen bond prevents unproductive
decomposition of H 2 O 2 . A similar η 1 -hydroperoxide intermediate and formation of 2 products by 2 parallel
ways have been assumed for various complexes. 49−51 The structure of the active species for oxidation of
ethylbenzene is different from that for the decomposition of H 2 O 2 . The active species for decomposition
of H 2 O 2 has a dimeric ( µ − η 1 : η 1 -peroxo) dimanganese(III) structure; 52 this conclusion was supported
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GHORBANLOO et al./Turk J Chem
by other works. 53,54 Ito et al.
suggested that there may be another peroxide adduct in the solution of
1
H 2 O 2 and it has η coordination mode, 55 as shown in Scheme 3. Since the oxidation of ethylbenzene with
the Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ]/H 2 O 2 system was decreased by the presence of a 10 equiv. radical
scavenger hydroquinone, it was concluded that the breaking of the oxidation of the ethylbenzene with H 2 O 2
is supposed to occur by free radical mechanism, yielding primarily ethylbenzene hydroperoxide. A simplified
pathway for the oxidation of ethylbenzene by H 2 O 2 in the presence of Mn complex is shown in Scheme 4.
OH
OH
O OH
O OH 2
N
II
O
OH 2
Mn
O
N
O
H 2O
Mn
O
N
H2 O O
O
O
O
Mn
O
N
H2 O O
Fe
Fe3O
44
3O
O
OH 2
Mn
O
O
H 2O
III
H 2O2
Si
O
Fe3O4
Si
O
O
O
O
H2O 2
OH
O
OO
O
H
N
OOH
III
O
OH 2
Mn
-H2O
O
O
H 2O
Mn
O
N
H2 O O
O
-MeOH
O4
FeFe33O
4
HO
MnIII-OOH
O
O
Si
O
O
O
Scheme 2. Proposed mechanism for the oxidation of ethyl benzene with H 2 O 2 over Fe 3 O 4 @SiO 2 /complex.
2.5. Catalyst recycling
As reported previously, 3 the catalyst including Fe 3 O 4 can be separated from the reaction mixture by a magnet
without loss of the catalyst. The recovery and reusability of Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ] catalyst were
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GHORBANLOO et al./Turk J Chem
O
O
H
O
N
H
O
O
O
H 2C
Mn
Mn
Mn
O
O
Mn
a
b
a (µ − η : η -peroxo) dimanganese(III) , b η 1 coordination mode.
1
1
Scheme 3. Proposed intermediate for a) oxidation reaction and b) decomposition of H 2 O 2 .
.
MnII(L)(HL)(H2O)2
MnIII(L)(HL)(H2O)(OH)+ OH
MnIII(OOH)(L)(HL)(H2O) + H2O
MnIII(L)(HL)(H 2O)(OH)+ H2O 2
.
MnIII(OOH)(L)(HL)(H 2O)
.
MnII(L)(HL)(H 2O)2 + OOH
.
OOH
OH + 1/2 O 2
.
.
OH +
.
OOH
+ MnIII(OOH)(L)(HL)(H2O)III(OOH)
OOH
- H 2O
O
_ MeOH
O
+ MnIII(OOH)
HO
+ MnII(L)(HL)(H2O)2
O
Scheme 4. Simplified pathway for the oxidation of ethylbenzene by H 2 O 2 in the presence of Mn complex.
investigated by the oxidation of methyl phenyl sulfide as a model reaction. Catalyst recycling experiments were
carried out by fixing the catalyst magnetically at the bottom of the flask and the solution was decanted after
each run. The solid left was washed with MeCN twice, and fresh substrate dissolved in MeCN was introduced
into the flask, allowing the system to proceed for the next run. The catalyst was reused 5 times without any
499
GHORBANLOO et al./Turk J Chem
perceptible loss of its catalytic activity, as shown in Table 9. ICP-AES analysis showed that no leaching was
observed on the solution phase in the next runs. This catalyst has some remarkable features including ease of
separation by an external magnet and, in contrast to other reported similar catalysts, no regeneration process
is required after each reaction. 56
Table 9. Effect of Fe 3 O 4 @SiO 2 [([Mn 2 L(HL)(H 2 O) 4 ] catalyst recycling on sulfoxidation. a
Number of recycles
Fresh
1
2
3
4
5
a
Conversion (%)
75
73
72
74
71
Selectivity to sulfoxide
100
100
100
100
100
100
Reaction conditions: a) catalyst Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]) (0.0018 mmol catalyst); methyl phenyl sulfide
1 mmol, CH 3 CN 2 mL, temperature 60 ± 1
◦
C, reaction time 1 h, H 2 O 2 3 mmol.
3. Conclusions
In summary, the present study has described the immobilization of [Mn 2 (HL) 2 (H 2 O) 4 ] onto a modified
magnetic nanoparticle surface. A range of characterization techniques confirm that the metal complex is
attached to the magnetic nanoparticle support. Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ] provides heterogeneous
catalysts for oxidation of sulfides and hydrocarbons by H 2 O 2 . Several factors such as amount of oxidant, type of
solvents, and temperature of the reaction mixture affect the performance of this catalyst, and acetonitrile is the
solvent of choice. The supported catalyst Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]) gave low activity compared to
its homogeneous counterpart but it has higher activity and selectivity than bulk particles. Thus, the immobilized
catalyst could be easily recovered by easy magnetic decantation and reused at least 5 times without noticeable
loss of activity. This system could be useful for many other base-catalyzed oxidations.
4. Experimental
4.1. Materials and equipment
The starting materials and solvents were purchased from Merck and used as received. Aqueous 30% H 2 O 2 (10.9
mol/L) was used and its exact concentration was determined before use by titration with standard KMnO 4 .
Elemental analyses were conducted on a CHN PerkinElmer 2400 analyzer. FTIR spectra were recorded on a
PerkinElmer 597 spectrometer. Manganese content was determined by an inductively coupled plasma–atomic
emission spectrometer (ICP-Spectro Genesis). Magnetic measurements were performed on an MPMS XL7
magnetometer. A scanning electron micrograph of the MNPs was taken on a Philips XL 30 SEM instrument.
The reaction products of the oxidation were analyzed by an HP Agilent 6890 gas chromatograph, equipped
with an HP-5 capillary column (phenyl methyl siloxane 30 m × 320 µ m × 0.25 µ m) with a flame-ionization
detector.
4.2. Synthesis of Schiff base ligand (H 3 L)
Salicylaldehyde (0.244 g, 2.0 mmol) was dissolved in 10 mL of toluene and to this was added a mixture of
L-tyrosine (0.36 g, 2.0 mmol) and NaOH (0.08 g, 2.0 mmol) in 10 mL of toluene. The reaction mixture thus
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GHORBANLOO et al./Turk J Chem
obtained was refluxed for 2 h and then the resulting yellow solid was filtered, washed with methanol, and dried
to give the product, yield 88.0%. IR (KBr, cm −1 ) : 3208 (w) (O–H), 3026 (w), 2963 (w), 2930 (w), 1613 (vs)
(C=N), 1514 (m), 1455 (m), 1364 (m), 1332 (s), 1245 (s), 1100 (m), 842 (s), 740 (m), 650 (s), 576 (s), 530 (s),
493 (w), 434 (w).
4.3. Synthesis of the complex
The complex was synthesized according to our previous report. 20 For this purpose, a mixture of L -tyrosine
(0.36 g, 2.0 mmol) and NaOH (0.08 g, 2.0 mmol) in CH 2 Cl 2 (10 mL) was added to a solution of salicylaldehyde
(0.244 g, 2.0 mmol) in CH 2 Cl 2 (10 mL) and refluxed, whereupon the colorless solution rapidly turned yellow.
The mixture was refluxed for 2 h; then Mn(OAc) 2 .4H 2 O (2 mmol, 0.498 g) was added and the mixture was
stirred under reflux for 5 h. The light green precipitate was collected and washed with methanol and dried in
air. Yield: 0.5 g (67%). IR (KBr, cm −1 ): 3424 (br), 3077 (w), 3035 (w), 2921 (m), 2854 (w), 1648 (vs), 1589
(vs), 1549 (w), 1515 (m), 1471 (s), 1444 (s), 1385 (s), 1280 (m), 1187 (m), 823 (m), 757 (s), 526 (m), 449 (m).
4.4. Synthesis of magnetite nanoparticles
Magnetic nanoparticles, Fe 3 O 4 , were prepared using the procedure reported by Wang et al. 43 Briefly, 0.04
mol of FeCl 3 .6H 2 O and 0.02 mol of FeCl 2 .4H 2 O were dissolved in 50 mL of 0.5 M HCl solution, which was
then added dropwise to 500 mL of 1.5 mol/L sodium hydroxide solution at 80 ◦ C under a nitrogen flow (40
mL/min) with vigorous stirring. The obtained Fe 3 O 4 nanoparticles were repeatedly washed with deionized
water followed by drying at 50 ◦ C under vacuum for 4 h. FTIR (KBr, cm −1 ) : 3400 (br), 580 (s).
Silica-coated magnetite nanoparticles (Fe 3 O 4 @SiO 2 ) were made by sol-gel method. 44 According to these
references, the magnetite nanoparticles (0.5 g) were dispersed in ethanol (50 mL). NH 4 OH (3 mL) and TEOS
(1 mL) were added successively. After stirring for 10 h, the black precipitate was collected with a permanent
magnet, and rinsed with ethanol 3 times. The product was dried and stored under vacuum conditions.
FTIR (KBr, cm −1 ): 3441 (br) (O–H), 1097 (vs), 921 (w), 817 (w), 577 (w), 477 (m), 434 (m).
4.5. Preparation of the supported complex
For immobilization of the complex, firstly we functionalized the Fe 3 O 4 @SiO 2 with a good linker such as
CPTMS. The functionalized Fe 3 O 4 @SiO 2 /CPTMS was prepared according to Saeedi et al. 36 According to
their report, Fe 3 O 4 @SiO 2 nanoparticles (1.0 g) were dispersed in dry toluene (30 mL) by sonication for 1 h.
Then 3-chloropropyltrimethoxysilane (1.8 mL, 10 mmol) was added and the reaction mixture was refluxed for
24 h under argon atmosphere. At the end of the reaction, the mixture was cooled to room temperature; the
products were adsorbed on a magnet and rinsed twice with dry toluene (100 mL) and twice with dry acetone
(100 mL). The obtained particles were dried under vacuum conditions. Linker loading = 1.43 mmol/g MNP
silica gel.
Then Fe 3 O 4 @SiO 2 /CPTMS (0.5 g) and [Mn 2 (LH) 2 (H 2 O) 4 ] (0.1 g) were refluxed in CH 2 Cl 2 for 24 h
and then washed with CH 2 Cl 2 for 4 h in order to eliminate all the [Mn 2 (LH) 2 (H 2 O) 4 ] complexes adsorbed
on the support. The brown material, Fe 3 O 4 @SiO 2 /[Mn 2 L(HL)(H 2 O) 4 ], was dried at room temperature and
characterized by CHN, SEM, ICP, IR spectroscopy, and VSM. Mn loading = 0.50 mmol/g MNP silica gel,
Complex loading = 0.25 mmol/g MNP silica gel. FTIR (KBr, cm −1 ) : 3445 (br, w), 2929 (w), 2861 (w), 1647
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GHORBANLOO et al./Turk J Chem
(s), 1596 (s), 1517 (w), 1471 (m), 1446 (m), 1388 (s), 1088 (vbr, vs), 825 (vs), 758 (m), 684 (w), 577 (s), 472
(s).
4.6. General oxidation procedure
Oxidation reactions were carried out under air at 60 ± 1 ◦ C with acetonitrile as solvent and aqueous 30% H 2 O 2
(10.9 M) as oxidant. In a typical experiment, a mixture of 0.0016 mmol of Fe 3 O 4 @SiO 2 /([Mn 2 L(HL)(H 2 O) 4 ]
as the catalyst, 3.0 mL of solvent, and 1.0 mmol of the sulfide were mixed in a 25-mL glass flask. After the
mixture was heated to 60 ◦ C, H 2 O 2 was added. At appropriate intervals, aliquots were removed and analyzed
immediately by GC. The oxidation products were identified by comparing their retention times with those of
authentic samples. Yields are based on the added substrate and were determined by a calibration curve.
Acknowledgments
The authors are thankful to the University of Zanjan for its financial support of this study.
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